CN101952371B - Surface-reacted precipitated calcium carbonate, process to make same, and uses thereof - Google Patents
Surface-reacted precipitated calcium carbonate, process to make same, and uses thereofDownload PDFInfo
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- CN101952371B CN101952371BCN2008801253503ACN200880125350ACN101952371BCN 101952371 BCN101952371 BCN 101952371BCN 2008801253503 ACN2008801253503 ACN 2008801253503ACN 200880125350 ACN200880125350 ACN 200880125350ACN 101952371 BCN101952371 BCN 101952371B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/02—Compounds of alkaline earth metals or magnesium
- C09C1/021—Calcium carbonates
- C09C1/022—Treatment with inorganic compounds
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/69—Water-insoluble compounds, e.g. fillers, pigments modified, e.g. by association with other compositions prior to incorporation in the pulp or paper
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paper (AREA)
Abstract
Description
The present invention relates to the technical field of the high BET specific surface area mineral filler based on precipitated chalk (PCC)---also referred to as synthetic calcium carbonate---.
This type of weighting agent can be used for a plurality of fields, comprises for paper (as weighting agent or coating pigment), cotton paper, coating, plastics, water treatment, particularly as the means except deasphalting and endocrine disrupting compounds (EDC).
Calcium carbonate mineral is divided into two classes usually: heavy (or natural) calcium carbonate (GCC) and precipitated chalk (PCC).
GCC is interpreted as a kind of calcium carbonate of natural existence form, picks up from sedimentogeneous rock as limestone or chalk, or picks up from rotten marble.GCC almost only has the calcite polymorphic, and it is stated to be triangle water chestnut square (rhombohedral), represents the most stable calcium carbonate crystal formation.
By contrast, except calcite, the calcium carbonate polycrystalline type thing of PCC class generally includes the even lower veterite class polymorphic than aragonite of the more unsettled aragonite class polymorphic with iris needle-like crystalline form and stability.Different PCC forms can be according to the characteristic peak identification of its x ray powder diffraction (XRD).
PCC is synthetic modal is to be undertaken by synthetic precipitin reaction, described reaction comprises a step that carbonic acid gas is contacted with aqua calcis, during the water suspension of the described aqua calcis formation calcium oxide of being everlasting most---also referred to as unslaked lime, its suspensoid often is called milk of lime---, provide.According to reaction conditions, described PCC can show as various ways, comprises stable and unsettled polymorphic form.In fact, PCC often represents a kind of calcium carbonate material of thermodynamic instability.
When mentioning in environment of the present invention, the carbonate synthesis calcium product that the implication of PCC is interpreted as being obtained by the carbonation of calcium hydroxide slurry, when described calcium hydroxide slurry, during from the finely divided calcium oxide particle in water, it often is called as lime white or milk of lime in the art.
Hereinafter will understand, clear superiority of the present invention is actual is that it has used a kind of PCC obtained by this class ordinary method.There is no doubt that, the technician will understand, and when when the lime white carbonating is formed to described PCC, can use other additive, deposition condition or implemented other steps before or after described precipitation; Yet the technician can be straightforward, can to any described PCC,---comprise only by the extremely strong PCC of alkalescence that a kind of carbonate-free lime slurry carbonating is obtained---and implement the advantage of the inventive method.
The calcium carbonate of finding GCC and PCC form can show different chemical property every now and then unexpectedly, usually can not in the application identical with PCC, use GCC, and vice versa.
For example, the following technology of having found record in EP 1 149 136 can not transfer to use PCC:
" water suspension of one or more pigment, weighting agent or mineral, described suspensoid can comprise a kind of polymer dispersant to stablize its rheological, and described suspensoid is characterised in that:
A) it comprises a kind of natural carbonate and described carbonate and gas CO2one or more reaction product and described carbonate and one or more in strong to strong H3o+one or more reaction product of ion donor, and
B) its pH measured under 20 ℃ is greater than 7.5.
While having found in the technology at EP 1 149 136 to use PCC to replace GCC (wherein GCC is as " natural carbonate "), particularly when by constantly adding H3o+ion donor produces CO2situation under while reappearing the technology of EP 1 149 136, the specific surface area of the product based on PCC of formation can not fully be expanded.
Why the technology of EP 1 149 136 is subject to special concern, actual is because it provides a kind of makes the surface structuration of described GCC and make the significantly method of increase of its specific surface area by being deposited on the GCC raw material of calcium salt of controlling at least part of crystallization, thereby the calcium source of described deposition material is described GCC material itself.
Yet, because this material of PCC can show some advantage with respect to GCC according to operability and concrete physical properties, the technician that expectation obtains above-mentioned high surface area material wishes again can the raw material of choice for use based on PCC, makes them need to find a kind of scheme and implement above-mentioned technology.
In the prior art, it should be noted that, introduce specific additive although lot of documents is paid close attention in the forming process of PCC, almost do not have document that the instruction of any relevant PCC PCC being used during the method for surface reaction occurs be completed into as adducts (adduct) is provided.
US 4,367, and 207 have described the ad hoc approach of a kind of PCC of preparation.Its proposition should be noted that the unreacted calcium hydroxide in all slurries that still are present in carbonating of neutralization, and can by for example adding the organic or inorganic polyprotonic acid of q.s,---to be citric acid, toxilic acid, oxysuccinic acid, propanedioic acid, phthalic acid, tartrate, boric acid, phosphoric acid, sulfurous acid or sulfuric acid---carry out in described neutralization.
WO 2005/123593 relates to a kind of method, wherein citric acid is mixed with a kind of calcium hydroxide slurry and makes described slurry carbonating to prepare a kind of PCC slurry, makes afterwards it dewater to prepare the PCC that a kind of high solids content forms.It proposes optionally to combine with dispersion agent or forms in PCC and add citric acid to the high solids content of preparation after adding dispersion agent, but this selection both be not further described and does not have example to be illustrated yet.In addition, it also points out that phosphoric acid can add in described PCC slurry with the given limit concentration of 0.8 % by weight that is no more than PCC weight, to maintain the surface-area of this PCC.
WO 2005/102931 has described a kind of method, wherein first part of organophosphate is added in calcium hydroxide slurry, then adds Tai-Ace S 150, and then adds CO2to form PCC.Afterwards, second part of organophosphate added in described PCC slurry, then make this slurry sieve and dewater to form dense PCC composition.As mentioned above, it has pointed out phosphoric acid and the described PCC slurry of limited amount that is no more than 1.5 % by weight of PCC weight to be mixed to stablize and maintain the surface-area of described PCC.
EP 0 406 662 has described a kind of method for preparing carbonate synthesis salt, and wherein pre-composition is by the CaCO of aragonite form3with lime, form: add a kind of " phosphoric acid derivatives " in this slurry, as phosphoric acid or its salt or various phosphoric acid salt, finally introduce CO2to carry out conventional carbonating.The purpose of this patent aims at and obtains a kind of PCC that can not industrially have special needle-like crystalline form before.Using phosphoric acid in EP 0,406 662 is the form in order by a kind of unidentified " calcium phosphate ", to produce specially described aragonite, and described " calcium carbonate " prepares new nucleation seed for required crystalline form.
The applicant finds by alkali (lime), to add calcium ion can not obtain the PCC of the surface reaction of needs in the method for EP 0 406 662.
In fact, when the applicant attempts implementing method that the calcium ion source wherein dissolved as described as EP 0 406 662 is calcium hydroxide, particularly when calcium hydroxide in wherein said when high-level, the applicant finds to have obtained a kind of like this material, wherein the calcium in the material of all at least part of crystallizations that form on surface is not to come from described PCC raw material, but comes from added calcium hydroxide.
US 5,043,017 has described the sour stabilization procedures of calcium carbonate, particularly PCC, described sour stabilization procedures is by being used a kind of calcium sequestrant and a kind of relevant conjugate base to carry out, described calcium sequestrant is hexa metaphosphoric acid calcium for example, and described conjugate base can be an alkali metal salt of a kind of weak acid (phosphoric acid, citric acid, boric acid, acetic acid etc.).In fact the requirement that, US 5,043, and 017 purpose and the present invention need to maintain the acid-respons of described PCC to produce the solubilize calcium ion---needing these ions to form a kind of crystallization that generates surface-area on the PCC surface---is fully contrary.
US 4, 244, 933 have described the calcium carbonate granule of the projection that contains a core and be located thereon, prepared by described particle: the first step by the following method, by a kind of water suspension of calcium hydroxide, from the top of a reactor, the direction with the carbon dioxide adverse current with being upward through described reactor sprays into described reactor, so that part calcium hydroxide is converted into calcium carbonate, follow second step, by the gained mixture, from another reactor head, the direction with the carbon dioxide adverse current with being upward through described reactor sprays into described reactor, to promote the carbonating of calcium hydroxide, carry out similarly the 3rd step, to complete carbonating, the wherein said the first step or second step are used phosphoric acid and water-soluble salt thereof.Described water-soluble salt is stated to be sodium salt, sylvite, zinc salt of phosphoric acid etc.
Finally, EP 1 769 035 discloses a kind of mineral color of drying, it is characterized in that described pigment contains a kind of product that original position forms by making between calcium carbonate and following material multiple reaction occurs:
Strong to strong H in-described carbonate and one or more3o+one or more reaction product of ion donor;
The gas CO that-described carbonate and original position form2and/or the gas CO of externally-originated supply2one or more reaction product;
The compound of-one or more formulas R-X.
But the document does not provide the further instruction of the surface reaction precipitated chalk that obtains high-specific surface area.
In a word, prior art:
-mostly pay close attention to and optimize the adducts used in the PCC forming process, rather than make established PCC contact to increase the BET specific surface area of this PCC with special additive;
-disclose when PCC and a kind of solubility acid or acid salt form negatively charged ion---its corresponding calcium salt has insoluble, as phosphoric acid---in conjunction with the time, do not mention the other means that required solubilize calcium ion is provided, and described negatively charged ion is only for the BET specific surface area that maintains PCC rather than the BET specific surface area of significantly expanding described PCC;
-disclose when PCC and solubility acid or acid salt form negatively charged ion---its corresponding calcium salt has insoluble, as phosphoric acid---in conjunction with the time, calcium ion is provided, can not produce required surface reaction PCC but the applicant is provided by the form that provides of these calcium ions.
Fully unexpectedly, control specific parameter in the procedure that the applicant finds to define hereinafter, particularly control one or more concrete obtainable solubilize calcium ions in some place in the method, the surface reaction precipitated chalk that forms high-specific surface area for success is very crucial.
That is, the applicant has researched and developed a kind of method for preparing the pigment of the precipitated chalk (PCC) that contains surface reaction, and the method comprises the following steps:
A) pigment that provides at least one to contain precipitated chalk (PCC);
B) provide H3o+ion;
C) negatively charged ion that provides at least one can form water-insoluble calcium salt, described negatively charged ion is dissolved in a kind of aqueous medium;
D) make pigment and the described H of the described PCC of containing3o+ion and contact to form a kind of slurry of the pigment that contains surface reaction PCC with the dissolved anion in described aqueous medium, the insoluble calcium phosphate of at least part of crystallization of the described negatively charged ion formed at least part of surface that a kind of PCC provided in a) in step is provided wherein said surface reaction PCC;
Described method is characterised in that in steps d) process in excessive solubilize calcium ion is provided,
With regard to the application, insoluble material is defined as a kind of like this material, and it obtains being less than or equal to the recovery solid material of 0.1g when with deionized water is mixed, being incorporated in 20 ℃ of lower filtered and recycled filtrate under 95 to 100 ℃ after described filtrate of evaporation 100g.Solubility (or dissolving) material is defined as under 95 to 100 ℃ and can reclaims and be greater than the material that 0.1g reclaims solid material after the described filtrate of evaporation 100g.
With regard to the application, described excessive solubilize calcium ion should corresponding to pass through H3o+ion dissolves the solubilize calcium Ion Phase of Nature creating in the PCC process than excessive solubilize calcium ion, wherein said H3o+ion only provides with the form of the gegenion of negatively charged ion, that is, by adding the negatively charged ion of sour form or non-calcium acid salt form, and do not exist any other calcium ion or calcium ion to produce source.
In steps d) process in the described excessive solubilize calcium ion that provides preferably by one or more following routes, provide:
Route IA: the solubility neutral salt or the acid salt that add calcium;
Route IIA: add original position to generate solubility neutral salt or the acid of acid salt or neutral salt or the acid salt of non-calcium of calcium.
Described H3o+ion can provide by one or more following routes:
Route IB: the acid or the acid salt that add described negatively charged ion;
Route IIB: add acid or the acid salt in order to all or part of described excessive solubilize calcium ion to be provided simultaneously.
For the present invention, " acid " is defined as Bronsted-Lowry acid, that is to say, it is a kind of H3o+ion donor." acid salt " is defined as the H partly neutralized with electropositive element3o+ion donor." salt " is defined as the electric neutrality ionic compound formed by negatively charged ion and positively charged ion." salt of partial crystallization " is defined as the salt that shows substantially discrete diffractogram under XRD analysis.
The material of the insoluble calcium phosphate that for the present invention, surface reaction PCC is a kind of at least part of crystallization that contains PCC and described dissolved anion.
In a preferred embodiment, described insoluble calcium phosphate stretches out from the surface of at least part of PCC.
Form the calcium ion of calcium salt of described at least part of crystallization of described negatively charged ion mainly from initial PCC material.
Do not wish to be limited to any theory, the applicant believes, in order to form the surface reaction calcium carbonate of high-specific surface area---calcium ion of insoluble calcium phosphate that wherein forms at least part of crystallization of described negatively charged ion is provided by the calcium carbonate initiator to a great extent---, not only need to discharge these calcium ions from described calcium carbonate, thereby can make described calcium ion maintain under the condition that enough mobilitys are precipitated out to carry out but also need to make this be released in, described precipitation is preferentially on established any calcium negatively charged ion crystallization of stretching out from the calcium carbonate surface, rather than disengaging on the calcium carbonate surface of these calcium ions, like this, be enough to be produced as the specific surface area that reaches required and before the calcium ion of the plane of crystal of needs therefrom discharging, described crystal will be by carbonate surface to outgrowth, and can not cover undissolved carbonate.
Do not wish to be limited to any theory, the applicant believes, by the lime white carbonating, synthetic PCC contains the unreacted hydrogen calcium oxide of double team at the PCC center, and they can migrate to each position along the PCC surface.The applicant's theory is, the calcium hydroxide on these PCC surfaces (or it is while being etched on the PCC surface, for example brings to surface when adding acid to be etched) forms a layer on this surface, in this layer, the calcium discharged and hydroxide ion and the calcium hydroxide that still is incorporated into the PCC surface reach balance.Applicant's theory is, strong to strong H in simple the introducing by using a kind of compound that also serves as negative ion source3o+in the situation of ion donor (hereinafter referred to as acid), as in EP 1 149 136, used H3pO4the time average case, acid can be when the PCC surface runs into hydroxide ion to be neutralized, the original position balance of the calcium hydroxide of calcium and hydroxide ion and surface bonding in the described PCC upper layer of this neutralization impact, thereby produce excessive calcium ion in the PCC surface, promote the rapid precipitation of calcium, and then the material that forms a kind of at least part of crystallization the next-door neighbour on the PCC surface is substantially to wrap up described PCC and to make it can reaction when further adding acid, and the material that can not make as desired at least part of crystallization continues outside surface growth and the restriction that exceeds this upper layer.
The applicant believes, thus need to by act on original position balance restriction in described layer wherein free concentration hydroxy prevent above-mentioned phenomenon, otherwise, described free hydroxide radical can in and PCC discharge the required H of calcium3o+ion, thereby the formation of prevention surface-area.The applicant finds, the concentration of the calcium ion that this can dissolve by increases realizes, by provide than the negatively charged ion by acid-salt or acid salt form the more solubilize calcium ion of solubilize calcium ion of independent generation realize.Be noted that Yu Qishuo these solubilize calcium ions that provide in addition are for directly forming the material of required at least part of crystallization, not equal to be that balance for guaranteeing the PCC surface can make constantly to obtain required calcium ion by PCC more.
The amount of the calcium hydroxide of the generation balance layer existed on the PCC surface changes with the synthesis condition of PCC.The amount of the solubilize calcium ion therefore, must adjusting provided in addition is to form specific surface area.
description a) to step: containing the pigment initiator of PCC
According to the step of the inventive method a), the pigment that a) provides at least one to contain precipitated chalk (PCC).
One of achievement of applicant is, it has been determined can be containing PCC pigment and negatively charged ion and H3o+produce the concrete reaction conditions of surface-area in the ion contact process by forming the calcium crystallization, wherein the calcium source is mainly the PCC starting raw material, the PCC had in step pigment a).In addition, when the applicant has determined in the pigment initiator PCC that uses arbitrary form, the method condition that can play a role, the PCC of described arbitrary form comprises the calcite polymorphic form, as the calcite of scalenohedron (scalenohedral) or water chestnut side's body, or metastable state six side's Vaterite and aragonites.
In fact, a) described of step containing the PCC in PCC pigment optionally at crystal modifier---as EDTA or other sequestrants---existence under synthetic.
Preferably, when wet grinding under the following conditions described during containing PCC pigment, observe degree that the pH of this wet grinding slurry rises than grinding larger that wherein said PCC all observes with the corresponding slurry of calcite GCC replacement, this proves that unreacted oxyhydroxide discharges from described PCC:
1) water that replaces described slurry with deionized water is to form a kind of slurry with 15 % by weight solid content features, and described solid content is measured according to the measuring method that hereinafter the embodiment part provides;
2) by step 1) slurry in a grinding chamber, use aluminum oxide that diameter is 1.0 to 1.6mm mill pearl to grind 180 minutes under 24 ℃ with the grinding rate of 2500rpm, the add-on of described slurry be can load described grinding chamber volume approximately 80%, the slurry recirculation rate is 700ml/ minute.
That is, according to the measuring method that hereinafter the embodiment part provides, measured, observe pH and raise in process of lapping over 2.
In a preferred embodiment, according to the measuring method that hereinafter embodiment partly provides, measure, the step described PCC contained in PCC pigment a) is wetting ability.
In a preferred embodiment, the step described PCC contained in PCC pigment a) is generated by the method that comprises at least one pulverising step.Pulverising step is defined as the mechanical processing steps that former particle diameter is reduced.Under the condition that this pulverising step for example can mainly be produced by a kind of collision of complementary object at refining effect, carry out, for example below one or more, in equipment, carry out: ball mill, rod mill, vibration mill, roller crusher, centrifugal impact mill, masher, pin rod pulverizer, hammer mill, pulverizer, pulverizer, de-clumper, cutting machine or other these kind equipments known to the skilled, or can under the condition that can carry out autogenous grinding, carry out.
In a preferred embodiment, according to the measuring method that hereinafter embodiment partly provides, measure, the step described weight median diameter containing the PCC in PCC pigment a) is 0.01 to 10 μ m, more preferably 0.5 to 2 μ m.
In an optional embodiment, the step described PCC pigment that contains a) also contains one or more following materials: talcum, clay, plastic hollow ball pigment or titanium dioxide.
In another embodiment, the described step PCC pigment that contains a) only consists of PCC.
In a preferred embodiment, the described step form with the water-based slurry containing PCC pigment a) provides.
In this preferred embodiment, as the measuring method according to hereinafter the embodiment part is provided is measured, at step c) before, the pH of described slurry preferably is less than 11, preferably is less than 10.5.
In this preferred embodiment, the described pigment containing PCC is optionally what disperse.But the conventional dispersion agent that operation technique personnel are known.Described dispersion agent can be anionic or cationic.A kind of preferred dispersion agent is based on polyacrylic dispersion agent.This type of dispersion agent preferably quantitatively adds to reach 0.35 % by weight of the described weight containing PCC pigment.
to step b) description: H3o+ion source
Step b according to the inventive method), provide H3o+ion.Described H3o+ion is for being partly dissolved PCC, thus the calcium ion that generation precipitates on the surface of PCC for the insoluble calcium phosphate that makes afterwards at least part of crystallization of negatively charged ion.
Described H3o+ion can provide by one or more following routes:
Route IB: the acid or the acid salt that add described negatively charged ion;
Route IIB: add simultaneously in order to acid or the acid salt of all or part of described excessive solubilize calcium ion to be provided, describedly provide excessive solubilize calcium ion by direct interpolation solubility calcium ion and/or by dissolving the PCC initiator, to discharge calcium ion and carry out.
In the situation that route IIB, the described while is preferably selected from order to acid or the acid salt that all or part of described excessive solubilize calcium ion is provided: the acid of sulfur-bearing is as sulfuric acid, hydrochloric acid, perchloric acid, formic acid, lactic acid, acetic acid, nitric acid, and their acid salt, for example their solubility calcium acid salt.
Particularly, described acid or acid salt are selected from acid (as sulfuric acid), hydrochloric acid, the acetic acid of sulfur-bearing, and their acid salt (as its solubility calcium acid salt).
Preferably, by described H3o+after ion adds in slurry, as the measuring method according to hereinafter embodiment partly provides, measure, the pH of described slurry temporarily is down to the value below 6.0.
to step c) description: the negatively charged ion that forms the insoluble calcium crystallization on PCC
Step c according to the inventive method), the negatively charged ion that provides at least one can form water-fast calcium salt, described negatively charged ion is dissolved in aqueous medium.Except described negatively charged ion, corresponding insoluble calcium phosphate also can comprise OH-ion and/or crystal water.
Step c) described negatively charged ion can add with the form of the neutral salt of solubility or acid salt, or adds with sour form, as long as it is in steps d) before and/or in process, be what to dissolve.
Described negatively charged ion can form (speciation) to the form of the additive of present method and produces by providing.For example, PO43-and HPO42-can be by adding H3pO4or H2pO4-salt produces.
Preferably, described negatively charged ion is selected from one or more following negatively charged ion: the negatively charged ion of phosphorous acid group is (as PO43-and HPO42-), oxalate negatively charged ion (C2o42-), CO32-form containing carbonate anion, phosphonate radical negatively charged ion, amber acid radical negatively charged ion or fluorine anion.More preferably, described negatively charged ion is selected from: the negatively charged ion of phosphorous acid group is (as PO43-and HPO42-), oxalate negatively charged ion (C2o42-), phosphonate radical negatively charged ion, amber acid radical negatively charged ion, fluorine anion.Most preferably, described negatively charged ion is phosphorous acid radical anion, as PO43-and HPO42-.
Using containing in the embodiment of carbonate anion, the described carbonate anion that contains can be by introducing gaseous state CO in slurry2original position produces.In the case, the technician can know how to implement described introducing to contribute to make CO2be converted into CO32-, for example, by selecting suitable temperature.
In a preferred embodiment, it is benchmark that the add-on of described negatively charged ion be take the weight of the described PCC that step provides in a), is 5 to 50 % by weight, preferably 15 to 30 % by weight.
to steps d) description: make with negatively charged ion, to contact containing PCC pigment
Steps d according to the inventive method), make described containing PCC pigment side by side or in different steps with described H3o+ion and contacting in water-based slurry environment with the negatively charged ion of described dissolving.
In a preferred embodiment, make described PCC and described H3o+after the ion contact, described negatively charged ion is contacted with described PCC.
In addition, the inventive method is characterised in that, in steps d) process in excessive solubilize calcium ion is provided.
Described excessive solubilize calcium ion preferably provides by one or more following routes:
Route IA: the calcium neutral salt or the acid salt that add solubility;
Route IIA: add acid or non-calcium neutral salt or acid salt that original position generates solubility calcium neutral salt or acid salt.
In the situation that pass course IA provides excessive solubilize calcium ion, it can be for example with CaCl2or Ca (NO3)2form add.
It is benchmark that the addition of described solubilize calcium ion be take the weight of the described PCC that step provides in a), preferably greater than or equal to 3 % by weight, preferably greater than or equal to 5 % by weight.
In a preferred embodiment, steps d) more than 50 ℃, preferably carry out at the temperature more than 60 ℃.
In a preferred embodiment, by steps d) slurry mix to form a kind of flowing of laminar flow that be essentially.
In an optional embodiment, steps d) under being selected from the existence of the compound of silicate, silicon-dioxide, alkali earth metal aluminate or their mixture, at least one carries out.
In an optional embodiment, described silicate is preferably selected from pure aluminium silicate or alkaline earth metal silicate.
In an optional embodiment, steps d) under existing, rare gas element carries out, and described indifferent gas passes in slurry.A kind of this type of gas can be CO2, as long as work as the technician, use CO2while making rare gas element, his capable of regulating slurry condition is to limit described CO2being converted into soluble carbonate salt gets final product.
In an optional embodiment, steps d) under the existence of another additive that can increase the slurry ionic strength, carry out, described additive is the non-calcium salt of inertia for example.Described salt comprises for example NaCl or KNO3.
In a preferred embodiment, the water of the PCC slurry of gained surface reaction can replace with deionized water.In a preferred embodiment, collect the water of described surface reaction PCC slurry, and make its recirculation enter method of the present invention with for all or part of solubilize calcium ion is provided.This merits attention especially when the inventive method is a kind of continuation method.
The surface reaction PCC slurry obtained can be concentrated, and optionally concentrated until obtain dry surface reaction PCC product.For desciccate, it can use fatty acid treatment in addition.For desciccate, it can wash with water in addition.
So, can obtain a kind of slurry of the pigment that contains surface reaction PCC, the insoluble calcium phosphate of at least part of crystallization that wherein said surface reaction PCC contains described negatively charged ion, stretch out on described at least part of surface containing the PCC in PCC pigment that it preferably provides a) from step.
This surface reaction PCC is characterised in that, its BET specific surface area is greater than after following situation the BET specific surface area obtained, that is: the identical PCC by step is provided in a) simultaneously or in different step with described step b) in identical dissolved anion and and H3o+the ion contact, so:
-H3o+ion only provides by adding described negatively charged ion, the described H provided3o+the molar weight of ion is less than or equal to the required molar weight of ionic charge of the described negatively charged ion of balance in theory; With
-do not use route IA and route IB.
In a preferred embodiment, the BET specific surface area of the PCC in the pigment that contains PCC that the BET specific surface area of the surface reaction PCC of gained and step provide in a) is compared at least large three times, more preferably large seven times.
Described BET specific surface area is all determined according to the measuring method that hereinafter embodiment partly defines with relevant all BET specific surface areas of the present invention.
In a preferred embodiment, according to the measuring method that hereinafter embodiment partly describes, measure, the solid content of the slurry that contains surface reaction PCC obtained is up to 25 % by weight, preferably 5 to 20 % by weight.
In a preferred embodiment, add a kind of dispersion agent in described slurry.
Preferably, during the described pigment that contains surface reaction PCC of wet grinding, observe in this wet grinding process under the following conditions, the pH of described wet grinding slurry at least raises 2:
1) water that replaces described slurry with deionized water is to form a kind of slurry with 15 % by weight solid content features, and described solid content is measured according to the measuring method that hereinafter the embodiment part provides;
2) by step 1) slurry in a grinding chamber, use aluminum oxide that diameter is 1.0 to 1.6mm mill pearl to grind 180 minutes under 24 ℃ with the grinding rate of 2500rpm, the add-on of described slurry is to make it fill approximately 80% of described grinding chamber volume, and the slurry cycle rate is 700ml/ minute.
In a preferred embodiment, according to the TGA measuring method that hereinafter embodiment partly describes, measure, the negatively charged ion calcium salt that described surface reaction PCC has: the mass ratio of calcium carbonate content is 5: 95 to 95: 5, preferably 20: 80 to 60: 40, and more preferably 25: 75 to 50: 50.
According to the measuring method that hereinafter embodiment partly provides, measure, the pore volume of described surface reaction PCC is preferably 1 to 2.2cm3/ g.
According to the measuring method that hereinafter embodiment partly provides, measure, the BET specific surface area of described surface reaction PCC is preferably 20 to 120m2/ g, preferably 55 to 115m2/ g, more preferably 60 to 100m2/ g.
While according to the measuring method that hereinafter embodiment partly provides, described surface reaction PCC being carried out to XRD analysis, described XRD analysis preferably illustrates the peak corresponding at least part of crystalline calcium of negatively charged ion.In a preferred embodiment, described salt comprises one or more following materials: octocalcium phosphate (OCP), hydroxylapatite (HAP) or tricalcium phosphate (TCP).
Described surface reaction PCC slurry can be used for paper, cotton paper, plastics, coating, water treatment and for removing the EDC compound.
Following examples example explanation the present invention, and do not limit its scope.
Embodiment
measuring method
Use following measuring method to determine the parameter provided in embodiment and claim.
The wetting ability of material
According to following test, material is divided into hydrophilic or non-hydrophilic.The following various water of preparation 50ml in the 100ml beaker: alcohol mixture: 100: 0,90: 10,80: 20,70: 30,60: 40,50: 50,40: 60,30: 70,20: 80,10: 90,0: 100.Then, make 0.5g material to be tried by the screen cloth (this screen cloth of jog therefrom passes through to guarantee all material, and described sieve aperture is sized to material slowly to be passed through under jog) that is positioned at beaker mouth top, and it is freely dropped on fluid surface.When screening completes, observed the material behavior on fluid surface in 5 minutes, as follows to the deciding grade and level of the material in each beaker:
The basic all material of 0=immersed in 30 seconds;
0.25=basic all material immersed in 5 minutes;
0.5=the material more than 50% immersed in 5 minutes;
0.75=the material more than 25% immersed in 5 minutes;
1=does not have weighting agent to immerse in 5 minutes substantially.
Draw specified rank with water: the graphic representation that proportion of ethanol changes.When the water for 100: 0 to 50: 50: when alcohol mixture, the value of observing are zero, material is divided into hydrophilic.
The pore volume of material
Suspensoid by material to be tried is made flap.Described flap forms as follows: suspensoid/slurry is applied to constant voltage a few hours, discharge moisture with the pore membrane filtration by 0.025 μ m, thereby form a kind of pigment flap of densification.Described flap is removed from device, and in the baking oven of 80 ℃ dry 24 hours.
After drying, porosity and the pore size distribution to the same position of each flap piece characterized by mercury porosimetry to use Micromeritics Autopore IV mercury porosimeter.The maximum impressed pressure of mercury is 414MPa, is equivalent to 0.004 μ m Laplce's throat diameter of (being about the nm level).The compression factor of mercury rate of compression, penetrometer rate of expansion and the sample solid phase that mercury penetration method is measured is proofreaied and correct.The more details of measuring method are recorded in Transport inPorous Media (2006) 63:239-259.
The specific surface area of material (SSA)
Sample, after 250 ℃ of lower heat treated 30 minutes, is used to the nitrogen measurement the specific area by the BET method according to ISO9277.Before measurement, by sample filtering, flushing and in the baking oven of 110 ℃ drying at least 12 hours.
The size distribution of granulated material (the quality % particle of diameter<X) and weight median particle (d50)
The sedimentation behavior that by settling process, the weight median particle of granulated material and particle diameter mass distribution are analyzed in gravity field is determined.Described measurement SedigraphtM5120 carry out.
Described method and instrument are known to the skilled, and are usually used in determining the particle diameter of weighting agent and pigment.Described measurement is at the Na of 0.1 % by weight4p2o7the aqueous solution in carry out.Use high speed agitator and ultrasonic wave dispersed sample.
X-ray diffraction (XRD)
The crystalline structure of material is determined based on XRD analysis utilization Brucker AXS:D8 Advance instrument, scans 2 to 70 ° of 2 θ, and scanning speed is 0.5 second/step, and step-length is 0.01 ° of 2 θ.Control spectrum PDF 2 databases based on joint committee (International Centre for Diffraction Data) issue are analyzed the gained spectrum.
The pH of water-based slurry
The pH Application standard pH meter of aqueous suspension is approximately being measured under 22 ℃.
The lift-off value of pH during the wet grinding material
The lift-off value of the pH observed during the wet grinding material is according to the following methods evaluation:
1) water that replaces slurry with deionized water is to form a kind of slurry with 15 % by weight solid content features, and described solid content is measured according to the measuring method that hereinafter embodiment partly provides;
2) by step 1) slurry in a grinding chamber, use aluminum oxide that diameter is 1.0 to 1.6mm mill pearl to grind 180 minutes under 24 ℃ with the grinding rate of 2500rpm, the add-on of described slurry is to fill approximately 80% of described grinding chamber volume, the slurry cycle rate is 700ml/ minute, and measures in time pH.
The solid content of water-based slurry
Described slurry solid content (also referred to as " dry weight ") is used the commercially available Moisture Analyser HR73 of Mettler-Toledo to determine, it is set as follows: temperature is 120 ℃, automatically closes shelves 3, standard drying, 5-20g slurry.
Calcium anion salt in material sample: the mass ratio of calcium carbonate
The calcium anion salt: the weight of the calcium carbonate in the material sample of the mass ratio of calcium carbonate based on drying and washing is determined, its by thermogravimetry (TGA) use Mettler ToledoTGA 851 adopt 500+/-the 50mg sample determination, the scanning temperature is as follows:
-with from 25 to 200 ℃ of the speed of 20 ℃/minute;
-maintain 15 minutes at 200 ℃;
-with from 200 to 400 ℃ of the speed of 20 ℃/minute;
-maintain 15 minutes at 400 ℃;
Airflow is that 80ml/min and nitrogen gas stream are 15ml/min.This test provides the CO discharged from sample2the quality of gas, based on this quality, can calculate the quality of calcium carbonate.The Mass Calculation value of this calcium carbonate and be equivalent to the quality of calcium anion salt to difference between sample quality.
the step preparation containing PCC pigment a)
Below to step used in follow-up test hereinafter described being described containing the preparation method of PCC pigment a).
The preparation of the slurry of the scalenohedron shape calcite PCC (PCC1) do not disperseed
PCC1 passes through CO2passing into a kind of calcium hydroxide slurry synthesizes to obtain a kind of slurry product, according to above-mentioned measuring method, measure, specific surface area and the weight median particle of described product are listed in table 1, and determine according to XRD analysis, and described product is mainly formed by the calcite phase of scalenohedron form.The slurry solid content is adjusted to 17 % by weight.According to above-mentioned measuring method, measure, the pH of this slurry is 8 to 9.5.
Afterwards, by the wet grinding of described PCC sample, with the variation according to above-mentioned test method measuring pH.In process of lapping, the pH that observes slurry has raise and has surpassed 2, higher than the lift-off value of the corresponding slurry that wherein surface reaction PCC all replaces with GCC.
In addition, this PCC sample is carried out to above-mentioned wetting ability test, determine that this sample is hydrophilic.
The preparation of the slurry of the scalenohedron shape calcite PCC (PCC2) disperseed
PCC2 passes through CO2pass in a kind of calcium hydroxide slurry and synthesize to obtain a kind of slurry product, according to above-mentioned measuring method, measure, specific surface area and the weight median particle of described product are listed in table 1, and determine according to XRD analysis, and described product is mainly formed by the calcite of scalenohedron form.Described slurry solids is adjusted under the existence of polyacrylate based dispersion agent to 40 % by weight.According to above-mentioned measuring method, measure, the pH of this slurry is 8 to 9.5.
Afterwards, by the wet grinding of described PCC sample, with the variation according to above-mentioned test method measuring pH.In process of lapping, the pH that observes slurry has raise and has surpassed 2, and higher than the lift-off value of the corresponding slurry that wherein surface reaction PCC is all replaced by GCC.
In addition, also above-mentioned PCC sample has been carried out to above-mentioned wetting ability test, determined that described sample has wetting ability.
The preparation of the slurry of the aragonite PCC (PCC3) do not disperseed
PCC3 passes through CO2pass in a kind of calcium hydroxide slurry and synthesize to obtain a kind of slurry product, measure according to above-mentioned measuring method, the specific surface area of described product and weight median particle are listed in table 1, and determine according to XRD analysis, and described product is mainly formed by the aragonite form.Slurry solids is adjusted to 17 % by weight.According to above-mentioned measuring method, measure, the pH of this slurry is 8 to 9.5.
Afterwards, by the wet grinding of described PCC sample, with the variation according to above-mentioned test method measuring pH.In process of lapping, observe slurry pH and raise and surpass 2, and higher than the lift-off value of the corresponding slurry that wherein surface reaction PCC is all replaced by GCC.
In addition, also described PCC sample has been carried out to above-mentioned wetting ability test, determined that described sample has wetting ability.
The preparation of the slurry of the water chestnut side bodily form PCC (PCC4) do not disperseed
PCC4 passes through CO2pass in a kind of calcium hydroxide slurry and synthesize to obtain a kind of slurry product, according to above-mentioned measuring method, measure, specific surface area and the weight median particle of described product are listed in table 1, and determine according to XRD analysis, and described product is mainly formed by water chestnut side's volume morphing.Slurry solids is adjusted to 17 % by weight.According to above-mentioned measuring method, measure, the pH of this slurry is 8 to 9.5.
Afterwards, by this PCC sample wet grinding, with the variation according to above-mentioned test method measuring pH.In process of lapping, observe slurry pH and raise and surpass 2, and higher than the lift-off value of the corresponding slurry that wherein surface reaction PCC is all replaced by GCC.
In addition, also this PCC sample is carried out to above-mentioned wetting ability test, determine that described sample has wetting ability.
embodiment 1
Following examples explanation prior art, comprise and make PCC pigment and H3o+with a kind of negatively charged ion that contains phosphate radical, under the condition that does not have other solubility calcium ion, contact.
In stainless steel reactor, by the solid content of regulating the PCC water-based slurry shown in following table, so that being 10% dry weight, the solid content of gained slurry prepares a kind of water-based slurry.Then, this slurry heated and maintain 70 ℃.
Take and form substantially under the condition of laminar flow, by H in stirring3pO4with 30 % by weight that are equivalent to PCC weight and be equivalent to approximately 3 * 10-3mole H3pO4the amount of/gram PCC added in the PCC slurry in 10 minutes.After adding, described slurry is stirred 5 minutes again.
Make gained slurry standing over night, then obtained product is filtered and drying.Measure the final specific surface area of this desciccate and be recorded in following table.
Table 1
embodiment 2
Following examples example explanation the present invention, comprise PCC1 is contacted under the existence of excessive solubility calcium ion with a kind of negatively charged ion that contains phosphate radical (providing with sour form), wherein when PCC contacts with the acid with corresponding soluble calcium salt or acid salt, produce the solubility calcium ion.
In stainless steel reactor, by the solid content of regulating above-mentioned PCC1 water-based slurry, so that being 10% dry weight, the solid content of gained slurry prepares a kind of water-based slurry.Then, this slurry is heated and maintains the temperature of reaction of " Tslurry " defined in following table.
Form substantially under the condition of laminar flow stirring take, will there is the H that the acid of corresponding soluble calcium salt or acid salt (additive 1) have given molar equivalent when being equivalent to contact precipitation calcium carbonate3o+the amount of ion/gram PCC (be equivalent to produce the solubilize calcium ion of given molar equivalent/gram PCC, these two kinds of set-point all are listed in the following table) adds in the PCC slurry.
Afterwards, by H3pO4with 30 % by weight that are equivalent to PCC weight and be equivalent to approximately 3 * 10-3mole H3pO4the amount of/gram PCC added in described PCC slurry in 10 minutes.After adding, described slurry is stirred 5 minutes again.Within this period, the pH that observes this slurry temporarily drops to the value lower than 6.0.
The final solid of resulting slurry is 8 to 12 % by weight.
Make gained slurry standing over night, then resulting product is filtered and drying.Measuring the final specific surface area of this desciccate is listed in following table.The test 1 of embodiment 1 also is listed in the following table as reference.
Table 2
*suppose that additive 1 all dissolves
In all cases, when the product that will obtain according to the inventive method carries out wet grinding according to aforesaid method, pH has raise and has surpassed 2 in the wet grinding process, higher than the lift-off value of the corresponding slurry that wherein surface reaction PCC is all replaced by GCC.
In all cases, when the product that will obtain according to the inventive method is analyzed according to above-mentioned TGA method, observe the calcium anion salt: the mass ratio of calcium carbonate is 20: 80 to 60: 40.
The XRD analysis of the product obtained according to the inventive method shows to exist calcium phosphate mineral substance and calcium carbonate.
embodiment 3
Following examples example explanation the present invention, comprise PCC1 is contacted under the existence of excessive solubility calcium ion with the negatively charged ion that contains phosphate radical (providing with sour form), wherein generation solubility calcium ion when PCC is contacted with the acid with corresponding soluble calcium salt or acid salt, and wherein said acid or acid salt and the negatively charged ion simultaneous quantitative that contains phosphate radical add.
In stainless steel reactor, by the solid content of regulating above-mentioned PCC1 water-based slurry, so that being 10% dry weight, the solid content of gained slurry prepares a kind of water-based slurry.Then, this slurry is heated and maintains the temperature of reaction of " Tslurry " defined in following table.
Form substantially under the condition of laminar flow stirring take, will there is the acid of corresponding soluble calcium salt or acid salt (additive 1) to be equivalent to have when the contact precipitation calcium carbonate H of given molar equivalent3o+the amount of ion/gram PCC (be equivalent to produce the solubilize calcium ion of given molar equivalent/gram PCC, these two kinds of set-point all are listed in the following table) adds in described PCC slurry.Simultaneously, by H3pO4with 30 % by weight that are equivalent to PCC weight and be equivalent to approximately 3 * 10-3mole H3pO4the amount of/gram PCC added in described PCC slurry in 10 minutes.After adding, the gained slurry is stirred 5 minutes again.Within this period, the pH that observes this slurry temporarily drops to the value lower than 6.0.
The final solid of the slurry obtained is 8 to 12 % by weight.
Make gained slurry standing over night, then resulting product is filtered and drying.Measuring the final specific surface area of this desciccate is listed in following table.
The test 1 of embodiment 1 also is listed in the following table as reference.
Table 3
| 10-3)** | ||
| Ca2+The equivalent mole number (* 10 of ion/gram PCC-3) | -- | 2.0 |
| Ca2+The equivalent quality (* 10 of ion/gram PCC-3) | -- | 80 |
| SSA(m2/g) | 50 | 115 |
*suppose that additive 1 all dissolves
In all cases, when the product that will obtain according to the inventive method carries out wet grinding according to aforesaid method, pH has raise and has surpassed 2 in the wet grinding process, higher than the lift-off value of the corresponding slurry that wherein surface reaction PCC is all replaced by GCC.
In all cases, when the product that will obtain according to the inventive method is analyzed according to above-mentioned TGA method, observe the calcium anion salt: the mass ratio of calcium carbonate is 20: 80 to 60: 40.
The XRD analysis of the product obtained according to the inventive method shows to exist calcium phosphate mineral substance and calcium carbonate.
embodiment 4
Following examples example explanation the present invention, comprise PCC1 contacted under the existence of excessive solubility calcium ion with the negatively charged ion that contains phosphate radical (providing with sour form), and wherein the solubility calcium ion is by adding the neutral calcium salt of a kind of solubility to provide.
In stainless steel reactor, by the solid content of regulating above-mentioned PCC1 water-based slurry, so that being 10% dry weight, the solid content of the slurry obtained prepares a kind of water-based slurry.Then, this slurry is heated and maintains the temperature of reaction of " Tslurry " defined in following table.
Form substantially under the condition of laminar flow stirring take, by the neutral calcium salt of a kind of solubility (additive 1) to be equivalent to the Ca of given molar equivalent2+the amount of ion/gram PCC (value be listed in the following table) adds in described PCC slurry.
Afterwards, by H3pO4with 30 % by weight that are equivalent to PCC weight and be equivalent to approximately 3 * 10-3mole H3pO4the amount of/gram PCC added described PCC slurry in 10 minutes.After adding, this slurry is stirred 5 minutes again.Within this period, the pH that observes this slurry temporarily drops to the value lower than 6.0.
The final solid of the slurry obtained is 8 to 12 % by weight.
Make gained slurry standing over night, then resulting product is filtered and drying.Measuring the final specific surface area of this desciccate is listed in following table.The test 1 of embodiment 1 also is listed in the following table as reference.
Table 4
*suppose that additive 1 all dissolves
In all cases, when the product that will obtain according to the inventive method carries out wet grinding according to aforesaid method, pH has raise and has surpassed 2 in the wet grinding process, higher than the lift-off value of the corresponding slurry that wherein surface reaction PCC is all replaced by GCC.
In all cases, when the product that will obtain according to the inventive method is analyzed according to above-mentioned TGA method, observe the calcium anion salt: the mass ratio of calcium carbonate is 20: 80 to 60: 40.
The XRD analysis of the product obtained according to the inventive method shows to exist calcium phosphate mineral substance and calcium carbonate.
embodiment 5
Following examples example explanation the present invention, comprise PCC1 is contacted under the existence of excessive solubility solubilize calcium ion with the negatively charged ion that contains phosphate radical (form with salt provides), wherein when PCC is contacted with the acid with corresponding soluble calcium salt or acid salt, produce the solubility calcium ion.
In stainless steel reactor, by the solid content of regulating above-mentioned PCC1 water-based slurry, so that being 10% dry weight, the solid content of the slurry obtained prepares a kind of water-based slurry.Then, this slurry is heated and maintains the temperature of reaction of " Tslurry " defined in following table.
Form substantially under the condition of laminar flow stirring take, will there is the H that the acid of corresponding soluble calcium salt or acid salt (additive 1) have given molar equivalent when being equivalent to contact precipitation calcium carbonate3o+the amount of ion/gram PCC (it is equivalent to produce the solubilize calcium ion of given molar equivalent/gram PCC, and these two kinds of set-point all are listed in the following table) adds in described PCC slurry.
Afterwards, by Na(3-x)hxpO4---wherein x=0-1 (value of x is pointed out in following table)---is to be equivalent to approximately 3 * 10-3mole Na(3-x)hxpO4the amount of/gram PCC added in described PCC slurry in 10 minutes.After adding, this slurry is stirred 5 minutes again.Within this period, the pH that observes this slurry temporarily drops to the value lower than 6.0.
The final solid of the slurry obtained is 8 to 12 % by weight.
Make gained slurry standing over night, then the product obtained is filtered and drying.Measuring the final specific surface area of this desciccate is listed in following table.The test 1 of embodiment 1 also is listed in the following table as reference.
Table 5
*suppose that additive 1 all dissolves
In all cases, when the product that will obtain according to the inventive method carries out wet grinding according to aforesaid method, pH has raise and has surpassed 2 in the wet grinding process, higher than the lift-off value of the corresponding slurry that wherein surface reaction PCC is all replaced by GCC.
In all cases, when the product that will obtain according to the inventive method is analyzed according to above-mentioned TGA method, observe the calcium anion salt: the mass ratio of calcium carbonate is 20: 80 to 60: 40.
The XRD analysis of the product obtained according to the inventive method shows to exist calcium phosphate mineral substance and calcium carbonate.
embodiment 6
Following examples example explanation the present invention, comprise PCC1 or PCC2 are contacted under the existence of excessive solubilized calcium ion with the negatively charged ion that contains phosphate radical (providing with sour form), generation solubility calcium ion while wherein contact under the existence of other the other additives that PCC and the acid with corresponding soluble calcium salt or acid salt had increase described slurry ionic concn.
In stainless steel reactor, making the solid content of the slurry that obtains by the solid content of regulating above-mentioned PCC1 or PCC2 water-based slurry is that 10% dry weight prepares a kind of water-based slurry.Then, this slurry is heated and maintains the temperature of reaction of " Tslurry " defined in following table.
Form substantially under the condition of laminar flow stirring take, will there is the H that the acid of corresponding soluble calcium salt or acid salt (additive 1) produce given molar equivalent when being equivalent to contact precipitation calcium carbonate3o+the amount of ion/gram PCC (it is equivalent to produce the solubilize calcium ion of given molar equivalent/gram PCC, and these two kinds of set-point all are listed in the following table) adds in described PCC slurry.
Continuing under stirring, the amount that following table is listed adds can increase the neutral solubilized salt of described slurry ionic concn (additive 2).
Afterwards, by H3pO4with 30 % by weight that are equivalent to PCC and be equivalent to approximately 3 * 10-3the amount of moles per gram PCC added in described PCC slurry in 10 minutes.After adding, this slurry is stirred 5 minutes again.Within this period, the pH that observes this slurry temporarily drops to the value lower than 6.0.
The final solid of the slurry obtained is 8 to 12 % by weight.
Make gained slurry standing over night, then the product obtained is filtered and drying.Measuring the final specific surface area of this desciccate is listed in following table.The test 1 of embodiment 1 also is listed in the following table as reference.
Table 6
| The molar equivalent (* 10 of PCC-3)** | ||||||
| Ca2+The equivalent mole number (* 10 of ion/gram PCC-3) | -- | 2.7 | 2.7 | -- | 2.7 | 2.7 |
| Ca2+The equivalent quality (* 10 of ion/gram PCC-3) | -- | 108 | 108 | -- | 108 | 108 |
| Additive 2 | -- | NaCl | KNO3 | -- | NaCl | KNO3 |
| % by weight with the additive 2 of PCC weighing scale | -- | 0.1 | 0.1 | -- | 0.1 | 0.1 |
| SSA(m2/g) | 54 | 61 | 75 | 18 | 48 | 45 |
*suppose that additive 1 all dissolves
In all cases, when the product that will obtain according to the inventive method carries out wet grinding according to aforesaid method, pH has raise and has surpassed 2 in the wet grinding process, higher than the lift-off value of the corresponding slurry that wherein surface reaction PCC is all replaced by GCC.
In all cases, when the product that will obtain according to the inventive method is analyzed according to above-mentioned TGA method, observe the calcium anion salt: the mass ratio of calcium carbonate is 20: 80 to 60: 40.
The XRD analysis of the product obtained according to the inventive method shows to exist calcium phosphate mineral substance and calcium carbonate.
embodiment 7
Following examples example explanation the present invention, comprise PCC3 is contacted under the existence of excessive solubility calcium ion with the negatively charged ion that contains phosphate radical (providing with sour form), wherein when PCC is contacted with the acid with corresponding soluble calcium salt or acid salt, produce the solubility calcium ion.
In stainless steel reactor, making the solid content of the slurry that obtains by the solid content of regulating above-mentioned PCC3 water-based slurry is that 10% dry weight prepares a kind of water-based slurry.Then, this slurry is heated and maintains the temperature of reaction of " Tslurry " defined in following table.
Form substantially under the condition of laminar flow stirring take, will there is the H that the acid of corresponding soluble calcium salt or acid salt (additive 1) have given molar equivalent when being equivalent to contact precipitation calcium carbonate3o+the amount of ion/gram PCC (it is equivalent to produce the solubilize calcium ion of given molar equivalent/gram PCC, and these two kinds of set-point all are listed in the following table) adds in described PCC slurry.
Afterwards, by H3pO4with 30 % by weight that are equivalent to PCC and be equivalent to approximately 3 * 10-3mole H3pO4the amount of/gram PCC added in described PCC slurry in 10 minutes.After adding, this slurry is stirred 5 minutes again.Within this period, the pH that observes this slurry temporarily drops to the value lower than 6.0.
The final solid of the slurry obtained is 8 to 12 % by weight.
Make gained slurry standing over night, then the product obtained is filtered and drying.Measuring the final specific surface area of this desciccate is listed in following table.
The test 2 of embodiment 1 also is listed in the following table as reference.
Table 7
*suppose that additive 1 all dissolves
In all cases, when the product that will obtain according to the inventive method carries out wet grinding according to aforesaid method, pH has raise and has surpassed 2, the lift-off value of the corresponding slurry all replaced by GCC higher than wherein said surface reaction PCC in the wet grinding process.
In all cases, when the product that will obtain according to the inventive method is analyzed according to above-mentioned TGA method, observe the calcium anion salt: the mass ratio of calcium carbonate is 20: 80 to 60: 40.
The XRD analysis of the product obtained according to the inventive method shows to exist calcium phosphate mineral substance and calcium carbonate.
embodiment 8
Following examples example explanation the present invention, comprise PCC2 is contacted under the existence of excessive solubility calcium ion with the negatively charged ion that contains phosphate radical (providing with sour form), wherein when PCC is contacted with the acid with corresponding soluble calcium salt or acid salt, produce the solubility calcium ion.
In stainless steel reactor, making the solid content of the slurry that obtains by the solid content of regulating above-mentioned PCC2 water-based slurry is that 10% dry weight prepares a kind of water-based slurry.Then, this slurry is heated and maintains the temperature of reaction of " Tslurry " defined in following table.
Form substantially under the condition of laminar flow stirring take, will there is the H that the acid of corresponding soluble calcium salt or acid salt (additive 1) have given molar equivalent when being equivalent to contact precipitation calcium carbonate3o+the amount of ion/gram PCC (it is equivalent to produce the solubilize calcium ion of given molar equivalent/gram PCC, and these two kinds of set-point all are listed in the following table) adds in described PCC slurry.
Afterwards, by H3pO4with 30 % by weight that are equivalent to PCC and be equivalent to approximately 3 * 10-3mole H3pO4the amount of/gram PCC added in described PCC slurry in 10 minutes.After adding, this slurry is stirred 5 minutes again.Within this period, the pH that observes this slurry temporarily drops to the value lower than 6.0.
The final solid of the slurry obtained is 8 to 12 % by weight.
Make gained slurry standing over night, then the product obtained is filtered and drying.Measuring the final specific surface area of this desciccate is listed in following table.
The test 2 of embodiment 1 also is listed in the following table as reference.
Table 8
| That number (* 10-3) | ||
| Ca2+The equivalent quality (* 10 of ion/gram PCC-3） | -- | 108 |
| SSA(m2/g) | 18 | 54 |
*suppose that additive 1 all dissolves
In all cases, when the product that will obtain according to the inventive method carries out wet grinding according to aforesaid method, pH has raise and has surpassed 2, the lift-off value of the corresponding slurry all replaced by GCC higher than wherein said surface reaction PCC in the wet grinding process.
In all cases, when the product that will obtain according to the inventive method is analyzed according to above-mentioned TGA method, observe the calcium anion salt: the mass ratio of calcium carbonate is 20: 80 to 60: 40.
The XRD analysis of the product obtained according to the inventive method shows to exist calcium phosphate mineral substance and calcium carbonate.
embodiment 9
Following examples example explanation the present invention, comprise PCC4 is contacted under the existence of excessive solubility calcium ion with the negatively charged ion that contains phosphate radical (providing with sour form), wherein when PCC is contacted with the acid with corresponding soluble calcium salt or acid salt, produce the solubility calcium ion.
In stainless steel reactor, making the solid content of the slurry that obtains by the solid content of regulating above-mentioned PCC4 water-based slurry is that 10% dry weight prepares a kind of water-based slurry.Then, this slurry is heated and maintains the temperature of reaction of " Tslurry " defined in following table.
Form substantially under the condition of laminar flow stirring take, will there is the H that the acid of corresponding soluble calcium salt or acid salt (additive 1) have given molar equivalent when being equivalent to contact precipitation calcium carbonate3o+the amount of ion/gram PCC (it is equivalent to produce the solubilize calcium ion of given molar equivalent/gram PCC, and these two kinds of set-point all are listed in the following table) adds in described PCC slurry.
Afterwards, by H3pO4with 30 % by weight that are equivalent to PCC and be equivalent to approximately 3 * 10-3mole H3pO4the amount of/gram PCC added in described PCC slurry in 10 minutes.After adding, this slurry is stirred 5 minutes again.Within this period, the pH that observes this slurry temporarily drops to the value lower than 6.0.
The final solid of the slurry obtained is 8 to 12 % by weight.
Make gained slurry standing over night, then the product obtained is filtered and drying.Measuring the final specific surface area of this desciccate is listed in following table.
The test 2 of embodiment 1 also is listed in the following table as reference.
Table 9
*suppose that additive 1 all dissolves
In all cases, when the product that will obtain according to the inventive method carries out wet grinding according to aforesaid method, pH has raise and has surpassed 2, the lift-off value of the corresponding slurry all replaced by GCC higher than wherein said surface reaction PCC in the wet grinding process.
In all cases, when the product that will obtain according to the inventive method is analyzed according to above-mentioned TGA method, observe the calcium anion salt: the mass ratio of calcium carbonate is 20: 80 to 60: 40.
The XRD analysis of the product obtained according to the inventive method shows to exist calcium phosphate mineral substance and calcium carbonate.
embodiment 10
Following examples example explanation the present invention, comprise PCC1 is contacted under the existence of excessive solubility calcium ion with the negatively charged ion that contains phosphate radical (providing with sour form), wherein when PCC is contacted with the acid with corresponding soluble calcium salt or acid salt, produce the solubility calcium ion.
In stainless steel reactor, making the solid content of the slurry that obtains by the solid content of regulating above-mentioned PCC1 water-based slurry is that 20% dry weight prepares a kind of water-based slurry.Then, this slurry is heated and maintains the temperature of reaction of " Tslurry " defined in following table.
Form substantially under the condition of laminar flow stirring take, will there is the H that the acid of corresponding soluble calcium salt or acid salt (additive 1) have given molar equivalent when being equivalent to contact precipitation calcium carbonate3o+the amount of ion/gram PCC (it is equivalent to produce the solubilize calcium ion of given molar equivalent/gram PCC, and these two kinds of set-point all are listed in the following table) adds in described PCC slurry.
Afterwards, by H3pO4with 30 % by weight that are equivalent to PCC weight and be equivalent to approximately 3 * 10-3mole H3pO4the amount of/gram PCC added in described PCC slurry in 10 minutes.After adding, this slurry is stirred 5 minutes again.Within this period, the pH that observes this slurry temporarily drops to the value lower than 6.0.
The final solid of the slurry obtained is 8 to 12 % by weight.
Make gained slurry standing over night, then the product obtained is filtered and drying.Measuring the final specific surface area of this desciccate is listed in following table.
The test 1 of embodiment 1 also is listed in the following table as reference.
Table 10
| Test | The present invention |
| Tslurry(℃) | 70 |
| Additive 1 | HCl |
| H3O+The molar equivalent (* 10 of/gram PCC-3)** | 5.5 |
| Ca2+The equivalent mole number (* 10 of ion/gram PCC-3) | 2.7 |
| Ca2+The equivalent quality (* 10 of ion/gram PCC-3) | 108 |
| SSA(m2/g) | 88 |
*suppose that additive 1 all dissolves
In all cases, when the product that will obtain according to the inventive method carries out wet grinding according to aforesaid method, pH has raise and has surpassed 2, the lift-off value of the corresponding slurry all replaced by GCC higher than wherein said surface reaction PCC in the wet grinding process.
In all cases, when the product that will obtain according to the inventive method is analyzed according to above-mentioned TGA method, observe the calcium anion salt: the mass ratio of calcium carbonate is 20: 80 to 60: 40.
The XRD analysis of the product obtained according to the inventive method shows to exist calcium phosphate mineral substance and calcium carbonate.
Claims (70)
1. prepare a kind of method of the pigment that contains surface reaction precipitated chalk PCC, said method comprising the steps of:
A) pigment that provides at least one to contain precipitated chalk;
B) provide H3o+ion;
C) negatively charged ion that provides at least one can form water-insoluble calcium salt, described negatively charged ion is dissolved in a kind of aqueous medium;
D) make pigment and the described H of the described PCC of containing3o+ion and contact to form a kind of slurry of the pigment that contains surface reaction PCC with the dissolved anion in described aqueous medium, the insoluble calcium phosphate of at least part of crystallization of the described negatively charged ion formed at least part of surface that a kind of PCC provided in a) in step is provided wherein said surface reaction PCC;
It is characterized in that, in steps d) process in excessive solubilize calcium ion is provided.
2. the method for claim 1, is characterized in that, the pigment of the step described PCC of containing a) is hydrophilic.
3. the method for any one in claim 1 or 2, is characterized in that, the pigment of the step described PCC of containing a) is produced by the method that comprises at least one pulverising step.
4. the method for claim 3, is characterized in that, described pulverising step is the wet grinding step.
5. the method for claim 4, is characterized in that, it is larger that the pH rising degree of the wet grinding slurry that contains PCC pigment of observing is observed when grinding wherein said PCC all with the corresponding slurry of calcite GCC replacement.
6. the method for claim 4, is characterized in that, when the pigment of the described PCC of containing a) to step carries out wet grinding, the pH that observes the wet grinding slurry has raise and surpassed 2.
7. the method for any one in claim 1 or 2, is characterized in that, the weight median diameter of the pigment of the step described PCC of containing a) is 0.01 to 10 μ m.
8. the method for any one in claim 1 or 2, is characterized in that, the weight median diameter of the pigment of the step described PCC of containing a) is 0.5 to 2 μ m.
9. the method for any one in claim 1 or 2, is characterized in that, the pigment of the step described PCC of containing a) also comprises one or more following materials: talcum, clay, plasticity hollow ball pigment or titanium dioxide.
10. the method for any one in claim 1 or 2, is characterized in that, the pigment of the step described PCC of containing a) only is comprised of PCC.
11. in claim 1 or 2, the method for any one, is characterized in that, the pigment of the step described PCC of containing a) provides with the form of water-based slurry.
12. the method for claim 11, is characterized in that, at step c) before, the pH of described slurry is less than 11.
13. the method for claim 11, is characterized in that, at step c) before, the pH of described slurry is less than 10.5.
14. the method for claim 11, is characterized in that the pigment of the described PCC of containing disperses.
15. in claim 1 or 2, the method for any one, is characterized in that, step b) described H3o+ion provides by one or more following routes:
-route IB: the acid or the acid salt that add described negatively charged ion;
Acid or acid salt that-route IIB: add simultaneously in order to all or part of described excessive solubilize calcium ion to be provided---directly adds the solubility calcium ion and/or dissolves described PCC initiator to discharge calcium ion---.
16. the method for claim 15, it is characterized in that, in the situation that route IIB, the described while is in order to the acid that all or part of described excessive solubilize calcium ion is provided or acid, hydrochloric acid, perchloric acid, formic acid, lactic acid, acetic acid, the nitric acid that acid salt is selected from sulfur-bearing, and their acid salt.
17. the method for claim 16, is characterized in that described acid or acid salt are selected from the acid of sulfur-bearing, hydrochloric acid, acetic acid, and their acid salt.
18. the method for claim 16, the acid that it is characterized in that described sulfur-bearing is sulfuric acid.
19. the method for claim 16, is characterized in that described acid salt is solubility calcium acid salt.
20. the method for claim 11, is characterized in that, by described H3o+after ion is added in slurry, the pH of described slurry temporarily is down to the value below 6.0.
21. in claim 1 or 2, the method for any one, is characterized in that, step c) described negatively charged ion with the form of solubility neutral salt or acid salt or with sour form, add, as long as it is in steps d) dissolve before and/or in process.
22. in claim 1 or 2, the method for any one, is characterized in that, step c) described negatively charged ion be selected from one or more following materials: the negatively charged ion of phosphorous acid group, oxalate negatively charged ion, CO32-negatively charged ion, phosphonate radical negatively charged ion, amber acid radical negatively charged ion or the fluorine anion containing carbonate of form.
23. the method for claim 22, is characterized in that described negatively charged ion is selected from one or more following materials: the negatively charged ion of phosphorous acid group, oxalate negatively charged ion, phosphonate radical negatively charged ion, amber acid radical negatively charged ion or fluorine anion.
24. the method for claim 22, is characterized in that described negatively charged ion is selected from one or more following materials: the negatively charged ion of phosphorous acid group.
25. the method for claim 22, the negatively charged ion that it is characterized in that described phosphorous acid group is PO43-and HPO42-.
26. in claim 1 or 2, the method for any one, is characterized in that, when described negatively charged ion is while containing the negatively charged ion of carbonate, the described negatively charged ion containing carbonate by introducing gaseous state CO in slurry2original position produces.
27. in claim 1 or 2, the method for any one, is characterized in that, the weight of the described PCC that the addition of described negatively charged ion provides in a) with step is counted benchmark, is 5 to 50 % by weight.
28. in claim 1 or 2, the method for any one, is characterized in that, the weight of the described PCC that the addition of described negatively charged ion provides in a) with step is counted benchmark, is 15 to 30 % by weight.
29. in claim 1 or 2, the method for any one, is characterized in that, makes described PCC and described H3o+after the ion contact, described negatively charged ion is contacted with described PCC.
30. in claim 1 or 2, the method for any one, is characterized in that, in steps d) in the described excessive solubilize calcium ion that provides by one or more following routes, provide:
-route IA: the solubility neutral salt or the acid salt that add calcium;
-route IIA: add solubility neutral salt or the acid of acid salt or neutral salt or the acid salt of non-calcium that original position generates calcium.
31. the method for claim 30, is characterized in that, when described excessive solubilize calcium ion pass course IA provides, it is selected from one or more following material: CaCl2or Ca (NO3)2.
32. in claim 1 or 2, the method for any one, is characterized in that, it is benchmark that the addition of solubilize calcium ion be take the weight of the described PCC that step provides in a), for being more than or equal to 3 % by weight.
33. in claim 1 or 2, the method for any one, is characterized in that, it is benchmark that the addition of solubilize calcium ion be take the weight of the described PCC that step provides in a), for being more than or equal to 5 % by weight.
34. in claim 1 or 2, the method for any one, is characterized in that, steps d) at the temperature more than 50 ℃, carry out.
35. in claim 1 or 2, the method for any one, is characterized in that, steps d) at the temperature more than 60 ℃, carry out.
36. in claim 1 or 2, the method for any one, is characterized in that, by steps d) slurry mix to form laminar flow.
37. in claim 1 or 2, the method for any one, is characterized in that, steps d) under being selected from the existence of following compound, at least one carries out: the compound of silicate, silicon-dioxide, alkali earth metal aluminate or their mixture.
38. the method for claim 37, is characterized in that, described silicate is selected from a kind of pure aluminium silicate or a kind of alkaline earth metal silicate.
39. in claim 1 or 2, the method for any one, is characterized in that, steps d) under a kind of existence of rare gas element, carry out, described rare gas element passes in slurry.
40. in claim 1 or 2, the method for any one, is characterized in that, steps d) under a kind of existence of additive of the ionic strength that increases described slurry, carry out.
41. the method for claim 40, is characterized in that described additive is the non-calcium salt of a kind of inertia.
42. the method for claim 40, is characterized in that, described additive is selected from NaCl or KNO3, or its mixture.
43. in claim 1 or 2, the method for any one, is characterized in that, the water of described surface reaction PCC slurry replaces with deionized water.
44. the method for claim 43, is characterized in that, the calcium ion source of water in described method of removing is reintroduced back to.
45. in claim 1 or 2, the method for any one, is characterized in that, described method is a kind of continuation method.
46. in claim 1 or 2, the method for any one, is characterized in that, by steps d) the slurry of described surface reaction PCC concentrated.
47. in claim 1 or 2, the method for any one, is characterized in that, to steps d) in add a kind of dispersion agent in the described slurry that forms.
48. in claim 1 or 2, the method for any one, is characterized in that, by steps d) the slurry drying of described surface reaction PCC to obtain a kind of surface reaction PCC product of drying.
49. the method for claim 48, is characterized in that, described desciccate is processed with lipid acid in addition.
50. the method for claim 48, is characterized in that, described desciccate water rinses.
51. the slurry of a pigment that contains surface reaction PCC, is characterized in that, its method by any one in claim 1 to 47 obtains.
52. the slurry of the pigment that contains surface reaction PCC of claim 51, is characterized in that, the insoluble calcium phosphate of at least part of crystallization that described surface reaction PCC contains a kind of described negatively charged ion.
53. the slurry of the pigment that contains surface reaction PCC of claim 52, is characterized in that, stretch out on the surface of at least part of PCC of the pigment of the described PCC of containing that the described calcium salt of described negatively charged ion provides a) from step.
54. in claim 51 to 53, the slurry of the pigment that contains surface reaction PCC of any one, is characterized in that, described salt comprises one or more following materials: octocalcium phosphate, hydroxylapatite or tricalcium phosphate.
55. in claim 51 to 53, the slurry of the pigment that contains surface reaction PCC of any one, is characterized in that, the negatively charged ion calcium salt of described surface reaction PCC: the content mass ratio of calcium carbonate is 5:95 to 95:5.
56. in claim 51 to 53, the slurry of the pigment that contains surface reaction PCC of any one, is characterized in that, the negatively charged ion calcium salt of described surface reaction PCC: the content mass ratio of calcium carbonate is 20:80 to 60:40.
57. in claim 51 to 53, the slurry of the pigment that contains surface reaction PCC of any one, is characterized in that, the negatively charged ion calcium salt of described surface reaction PCC: the content mass ratio of calcium carbonate is 25:75 to 50:50.
58. the slurry of the pigment that contains surface reaction PCC of any one in claim 51 to 53, it is characterized in that, the BET specific surface area of described surface reaction PCC is greater than after following situation the BET specific surface area obtained, that is: the identical PCC that makes step provide in a) simultaneously or in different step with dissolved anion and and H identical in step b)3o+the ion contact, so:
-H3o+ion only provides by adding described negatively charged ion, the described H provided3o+the molar weight of ion is less than or equal to the required molar weight of ionic charge of the described negatively charged ion of balance in theory; With
-do not use following route IA and route IB:
-route IA: the solubility neutral salt or the acid salt that add calcium;
-route IB: the acid or the acid salt that add described negatively charged ion.
59. in claim 51 to 53, the slurry of the pigment that contains surface reaction PCC of any one, is characterized in that, the BET specific surface area of described surface reaction PCC is than step a) at least large three times of the BET specific surface area of PCC in the pigment that contains PCC that provides.
60. in claim 51 to 53, the slurry of the pigment that contains surface reaction PCC of any one, is characterized in that, the BET specific surface area of described surface reaction PCC is than step a) at least large seven times of the BET specific surface area of PCC in the pigment that contains PCC that provides.
61. in claim 51 to 53, the slurry of the pigment that contains surface reaction PCC of any one, is characterized in that, the BET specific surface area of described surface reaction PCC is 20 to 120m2/ g.
62. in claim 51 to 53, the slurry of the pigment that contains surface reaction PCC of any one, is characterized in that, the BET specific surface area of described surface reaction PCC is 55 to 115m2/ g.
63. in claim 51 to 53, the slurry of the pigment that contains surface reaction PCC of any one, is characterized in that, the BET specific surface area of described surface reaction PCC is 60 to 100m2/ g.
64. in claim 51 to 53, the slurry of the pigment that contains surface reaction PCC of any one, is characterized in that, the solid content of the described slurry that contains surface reaction PCC is for being up to 25 % by weight.
65. in claim 51 to 53, the slurry of the pigment that contains surface reaction PCC of any one, is characterized in that, the solid content of the described slurry that contains surface reaction PCC is 5 to 20 % by weight.
66. the slurry of the pigment that contains surface reaction PCC of any one in claim 51 to 53, it is characterized in that, when the described pigment that contains surface reaction PCC is carried out to wet grinding, the pH that observes the wet grinding slurry has raise at least 2 in described wet grinding process.
67. in claim 51 to 53, the slurry of the pigment that contains surface reaction PCC of any one, is characterized in that, the pore volume of described surface reaction PCC is 1 to 2.2cm3/ g.
68. the pigment that contains surface reaction PCC of a drying, is characterized in that, it is to be passed through the method acquisition of any one in claim 48 to 50 by the slurry of any one in claim 51 to 67.
69. the purposes of surface reaction PCC slurry in paper, plastics, coating or water treatment of any one in the surface reaction PCC of claim 68 or claim 51 to 67.
70. the purposes of claim 69, wherein said paper is cotton paper.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP07123077AEP2070991B1 (en) | 2007-12-12 | 2007-12-12 | Process to make surface-reacted precipitated calcium carbonate |
| EP07123077.5 | 2007-12-12 | ||
| US820807P | 2007-12-19 | 2007-12-19 | |
| US61/008,208 | 2007-12-19 | ||
| PCT/EP2008/066631WO2009074492A1 (en) | 2007-12-12 | 2008-12-02 | Surface-reacted precipitated calcium carbonate, process to make same, and uses thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101952371A CN101952371A (en) | 2011-01-19 |
| CN101952371Btrue CN101952371B (en) | 2013-12-11 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008801253503AExpired - Fee RelatedCN101952371B (en) | 2007-12-12 | 2008-12-02 | Surface-reacted precipitated calcium carbonate, process to make same, and uses thereof |
Country Status (17)
| Country | Link |
|---|---|
| US (2) | US10280309B2 (en) |
| EP (2) | EP2070991B1 (en) |
| JP (1) | JP5592266B2 (en) |
| KR (1) | KR101529356B1 (en) |
| CN (1) | CN101952371B (en) |
| AT (1) | ATE480597T1 (en) |
| BR (1) | BRPI0820919B1 (en) |
| CA (1) | CA2708091C (en) |
| DE (1) | DE602007009124D1 (en) |
| DK (2) | DK2070991T3 (en) |
| ES (2) | ES2352298T3 (en) |
| MY (1) | MY165935A (en) |
| PL (1) | PL2070991T3 (en) |
| PT (2) | PT2070991E (en) |
| RU (1) | RU2470052C2 (en) |
| TW (1) | TWI445771B (en) |
| WO (1) | WO2009074492A1 (en) |
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